CN105601868A - Rigid foam polyurethane thermal insulation material - Google Patents
Rigid foam polyurethane thermal insulation material Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
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- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
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- C08K3/34—Silicon-containing compounds
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- C08K7/00—Use of ingredients characterised by shape
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
The invention relates to a thermal insulation material and discloses a rigid foam polyurethane thermal insulation material. The thermal insulation material is prepared by mixing and foaming the following raw materials in parts by weight: 70-100 parts of isocyanate, 40-80 parts of polyether polyol I, 10-30 parts of polyether polyol II, 3-6 parts of expanded vermiculite, 5-8 parts of nano silicon dioxide, 10-20 parts of foaming agent, 1-5 parts of catalyst and 1-5 parts of 3-[polyethylene glycol methyl ether]propyl trialkoxy silane, wherein the polyether polyol I is lignin polyether polyol; and the polyether polyol II is polyether polyol polymerized by taking modified peanut oil as an initiator and epoxy propane as a polymerization monomer. The thermal insulation material has high compressive strength, tensile strength and impact strength and avoids the phenomena of deformation, bulging, barring and even cracking of a water tank.
Description
Technical field
The present invention relates to insulation material, relate in particular to a kind of hard-foam polyurethane insulation material.
Background technology
The continuous increase of and environmental protection pressure day by day in short supply along with the energy, countries in the world all start to try hard to recommend exploitation renewable energySource, wherein solar energy is to utilize and exploitation is the widest, the best regenerative resource of development prospect, has now been widely used in each row eachIndustry, solar water heater industry is exactly one of them. China's solar energy resources that is richly stored with, solar energy utilizes prospect wideWealthy, be at present in the world solar water heater first use state and producing country.
As everyone knows, concerning solar water heater, the selection of water tank heat preserving material is vital, can be used as at presentThe insulation material of water tank mainly contains polyurethane foam, phenol formaldehyde foam, superfine fibre etc. Polyurethane foam is with poly-by isocyanatesEther composition mixing is poured into foaming in mould or water tank cavity and makes, and wherein polyether composition contains PPG, foamingAgent, catalyst, curing agent, fire retardant, stabilizing agent etc., because polyurethane foam has, moulding process is simple, thermal conductivity factor is low etc.Advantage is the insulation material that water tank mainly adopts.
In lignin structure, contain alcoholic extract hydroxyl group, can react and prepare polyurethane with isocyanates by Substitute For Partial polyalcoholHard bubble, but because hydroxy radical content is lower, cause its activity lower, limited its application; In addition, in the mistake of preparing polyurethane foamCheng Zhong, is woodenly usually dispersed in the middle of polyalcohol with macromolecular particle form, causes the decline of reactivity worth and abscess notEvenly, so want a large amount of lignin that use in polyurethane, just must resolve the problems of dissolution of lignin.
The main molecules of vegetable oil consists of triacylglycerol ester, also have a small amount of free fatty and partial glyceride,Phosphatide, tocopherol and the vitamin E of 0.1-0.5%. In general, the oleic acid content in vegetable oil is higher, linoleic acid plus linolenic acidContent is lower, and its oxidation stability is better. In vegetable oil molecule, contain a large amount of carbon-carbon double bonds, the oxidation mechanism of vegetable oil is mainShow as active allyl reaction, this is the poor main cause of its oxidation stability just. Vegetable oil major part is by stablizing raw materialObtaining, is therefore a kind of worthwhile urethane raw, and shortcoming is that it lacks and the necessary active hydrogen of isocyanate reaction, therefore needTo carry out modification to vegetable oil.
Polyurethane hard foam in process of production, because of itself characteristic, production technology and direct labor's operative skill etc.The reason of each side, the problem of ubiquity foam contraction, easily causes foam and housing parts to come off or all come off, finalCause casing deformation, vacuum mouth of pipe foam cracking, What is more, and the polyurethane hard foam between inner bag and shell is horizontal or longitudinalFtracture, reduced widely the heat insulation effect of water tank.
Summary of the invention
Goal of the invention of the present invention is: for the problem of above-mentioned existence, provide a kind of hard-foam polyurethane insulation material. ShouldHard-foam polyurethane insulation material has the better mechanical property such as compression strength, hot strength, has overcome foaming simultaneouslyThe shortcoming that after-contraction is large, avoids water tank distortion, rises and heave the stupefied even phenomenon of cracking, and ensured the insulation of water-heater water tankPerformance.
The present invention is achieved by the following technical solutions:
A kind of hard-foam polyurethane insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction: isocyanide70 ~ 100 parts of acid esters, 40 ~ 80 parts of PPG I, 10 ~ 30 parts of PPG II, 3 ~ 6 parts of expanded vermiculites, nanometer titanium dioxide5 ~ 8 parts of silicon, 10 ~ 20 parts of blowing agents, 1 ~ 5 part of catalyst, 3-[MPEG-550] 1 ~ 5 part of propyl trialkoxy silane;Described PPG I is lignin polyether polyalcohol, and described PPG II is is initiator, epoxy by modification peanut oilPropane is the PPG that polymerization single polymerization monomer is polymerized.
Further, described isocyanates is dimer acid diisocyanate, 1, hexamethylene-diisocyanate, toluene diisocynateOne or more in ester or '-diphenylmethane diisocyanate.
Further, the particle diameter of described expanded vermiculite is 40 ~ 70 orders.
Further, described nano silicon is nanometer silica line or hollow mesoporous silica nanospheres.
Further, described blowing agent is a fluorine dichloro hexane, F-11, dichlorodifluoromethane, a chlorine difluoroOne or more in ethane and chloro fluoroethane.
Further, described catalyst is diethanol monoisopropanolamine or AEEA.
Further, the degree of functionality of described PPG I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and it is pressedRaw material and method according to following parts by weight are made:
(1) take 50 ~ 100 parts, lignin, 30 ~ 50 parts, water, 1 ~ 5 part of lignin peroxidase, 1 ~ 3 part of catalase, furanMutter 3 ~ 10 parts of 1 ~ 10 part, acetaldehyde and furfuryl alcohols in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modifiedLignin;
(2) by 100 parts, enzymolysis modified lignin, 250 ~ 350 parts of glycerine, 100 ~ 300 parts of diethylene glycol (DEG)s and Pd-Fe catalyst 0.01~ 0.05 part is mixed in reactor, and controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then takes out trueSky, adds 2 ~ 10 parts of expoxy propane, and atmospheric closed reaction 2 hours, obtains described PPG I.
Further, the degree of functionality of described PPG II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, itsMake according to the raw material of following parts by weight and method:
(1) take in 1 ~ 5 part to 100 ~ 300 portions peanut oil of 20 ~ 50 parts of ethylene glycol and magnesium chloride, controlling reaction temperature is 120 DEG C,React 3 hours, obtain modification peanut oil;
(2) 0.05 ~ 1.0 part of 100 parts of modification peanut oil and Pd-Fe catalyst is mixed in reactor, controls reaction temperature and be150 DEG C, reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add 2 ~ 10 parts of expoxy propane, atmospheric closed reaction 2Hour, obtain described PPG II.
The present invention adopts lignin polyether polyalcohol to react and prepare hard polyurethane foam with isocyanates, increases polyurethaneThe hard bubble intensity of insulation material. In system, the hydroxyl of lignin can with isocyanate reaction, obtain lignin-base polyurethane.Lignin is to have macromolecular compound cancellated, that contain the firm groups such as phenyl ring, in hard polyurethane foam, can increaseAdd the intensity of foam. Therefore, with respect to hard bubbling (PPG serves as soft section therein) of being prepared by common PPG, thisPlant lignin-base polyurethane foamed material better in the performance of the aspect such as hot strength, compression strength.
It is that initiator, expoxy propane are that the polyethers that is polymerized of polymerization single polymerization monomer is polynary that part of the present invention adopts modification peanut oilAlcohol, peanut oil structure is carried out after modification, can on strand, introduce a large amount of hydroxyls, the PPG degree of functionality preparingHeight, hydroxyl value is high; It can react with isocyanates is full and uniform in system, and promotes other auxiliary agent evenly mixing in reactantClose dispersion, generate the fine and closely woven abscess that is evenly distributed, reduce the shrinkage factor after foam-formed; Simultaneously because modification peanut oil is renewableResource, thus the use of petroleum derivative indirectly reduced, reduce the dependence to petroleum resources, can serve as novel foamRaw material.
Expanded vermiculite is a kind of secondary metamorphic mineral of water aluminosilicate containing magnesium of layer structure, and raw ore is outer like mica, itsFor by fabric and raw-vermiculite sheet after high-temperature roasting, its volume energy vermiculite obtaining after several times to tens times that expands rapidly. After expandedVermiculite is graininess, have heat insulation, resistance toly freeze, the excellent properties such as antibacterial, fire prevention, sound absorption, what the present invention adopted is that particle diameter is 40 ~ 70 ordersExpanded vermiculite, the percent opening of the increase polyurethane hard foam that expanded vermiculite can be suitable, and can delay foamable gel and solidify speedDegree, prevents that foam from greatly easily pushing inner bag and outer wall because of short time inner accumulated strength, reduces the generation of " bad foam ", simultaneouslyReduce the shrinkage factor after foam-formed.
Nano silicon is a kind of Inorganic Non-metallic Materials of excellent performance, and it is large that it has specific area, adsorptionPower is strong, the special performances such as chemical purity is high, dispersive property good, thermal resistance, with its superior stability, reinforcement, thickening property andThixotropy shows unique characteristics in numerous subjects and field, has the effect of not replacing. The nano silicon adopting is hereinNanometer silica line or hollow mesoporous silica nanospheres, after foaming raw material mixes, nano silicon can be distributed in bubbleIn the skeleton of hole wall, foamed material, play the effect that strengthens hole wall and foam stiffness, and can not affect foam structure, mix simultaneouslyAssorted nano silicon also can improve the intensity of hard-foam polyurethane insulation material.
The foam stabiliser that the present invention adopts is 3-[MPEG-550] propyl trialkoxy silane, it can reduceThe surface tension of urethane raw mixture, is raised up between the maturation period at foam, prevents the thermodynamics of foam by surface tensionThe material that unstable state occurs.
After hard polyurethane foam formula material mixing jetting of the present invention, can make formation of foam spherical or oval spherical and distributeEvenly fine and closely woven abscess, expanded material heat-insulating property is stable, and increases the intensity of cell wall, reduces when foam-formed because of interior external pressureThe poor material compression phenomena occurring suitably increases the percent opening of foam simultaneously, reduces the shrinkage factor after foam-formed.
In sum, owing to having adopted technique scheme, the invention has the beneficial effects as follows:
(1) the present invention adopts lignin polyether polyalcohol in foaming formulation, the lignin-base rigid foam material making and tradition sideThe prepared foamed material of method is compared, and has better compression strength, hot strength and impact strength.
(2) hard-foam polyurethane insulation material of the present invention compared with prior art, except possessing conventional polyurethanes foamed materialOutside high heat preservation performance, also reduce and made because of each side reasons such as itself characteristic, production technology and direct labor's operative skillsThe foam contraction problem becoming, avoids water tank distortion, rises and heave the stupefied even phenomenon of cracking.
Detailed description of the invention
Disclosed all features in this description, or step in disclosed all methods or process, except mutually exclusiveFeature and/or step beyond, all can combine by any way.
Disclosed arbitrary feature in this description (comprising any accessory claim, summary), unless narration especially all canReplaced by other equivalences or the alternative features with similar object. ,, unless narration especially, each feature is a series ofAn example in equivalence or similar characteristics.
Embodiment 1
First prepare PPG I, process is as follows:
(1) take lignin 80g, water 40g, lignin peroxidase 5g, catalase 1g, furans acetaldehyde 1g and furfuryl alcohol 5gIn reactor, reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 300g, diethylene glycol (DEG) 200g and Pd-Fe catalyst 0.03g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane8g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 4.6, the described PPG I that hydroxyl value is 400mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 40g and magnesium chloride 3g in 200g peanut oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification peanut oil;
(2) modification peanut oil 100g and Pd-Fe catalyst 0.08g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 8g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.6, the described PPG II that hydroxyl value is 370mgKOH/g.
A kind of hard-foam polyurethane insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction:Take PPG I 40g, PPG II 10g, expanded vermiculite 3g, nanometer silica line 5g, a fluorine dichloro hexane10g, diethanol monoisopropanolamine 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mixes, then withDimer acid diisocyanate 80g mixed foaming can obtain hard-foam polyurethane insulation material of the present invention after overcuring.
Embodiment 2
First prepare PPG I, process is as follows:
(1) take lignin 50g, water 30g, lignin peroxidase 3g, catalase 2g, furans acetaldehyde 3g and furfuryl alcohol10g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 250g, diethylene glycol (DEG) 100g and Pd-Fe catalyst 0.01g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane4g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 5.0, the described PPG I that hydroxyl value is 400mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 20g and magnesium chloride 1g in 100g peanut oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification peanut oil;
(2) modification peanut oil 100g and Pd-Fe catalyst 0.05g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 4g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.5, the described PPG II that hydroxyl value is 390mgKOH/g.
A kind of hard-foam polyurethane insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction:Take PPG I 40g, PPG II 10g, 40 order expanded vermiculite 3g, nanometer silica line 5g, trichloro-monofluoro firstAlkane 10g, AEEA 2g and 3-[MPEG-550] propyl trialkoxy silane 2g mixes, then with 1,Hexamethylene-diisocyanate 80g mixed foaming can obtain hard-foam polyurethane insulation material of the present invention after overcuring.
Embodiment 3
First prepare PPG I, process is as follows:
(1) take lignin 100g, water 50g, lignin peroxidase 2g, catalase-3 g, furans acetaldehyde 8g and furfuryl alcohol6g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(2) enzymolysis modified lignin 100g, glycerine 350g, diethylene glycol (DEG) 250g and Pd-Fe catalyst 0.05g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane10g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 4.7, the described PPG I that hydroxyl value is 410mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 50g and magnesium chloride 5g in 300g peanut oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification peanut oil;
(2) modification peanut oil 100g and Pd-Fe catalyst 1.0g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 8g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 6.0, the described PPG II that hydroxyl value is 350mgKOH/g.
A kind of hard-foam polyurethane insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction:Take PPG I 80g, PPG II 20g, 60 order expanded vermiculite 6g, nanometer silica line 8g, difluoro dichloromethaneAlkane 20g, AEEA 5g and 3-[MPEG-550] propyl trialkoxy silane 4g mixes, then with firstPhenylene diisocyanate 100g mixed foaming can obtain hard-foam polyurethane insulation material of the present invention after overcuring.
Embodiment 4
First prepare PPG I, process is as follows:
(1) take lignin 80g, water 40g, lignin peroxidase 1g, catalase-3 g, furans acetaldehyde 10g and furfuryl alcohol5g is in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modified lignin;
(3) enzymolysis modified lignin 100g, glycerine 300g, diethylene glycol (DEG) 200g and Pd-Fe catalyst 0.03g are mixed in to reactionIn device, controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then vacuumizes, and adds expoxy propane8g, atmospheric closed reaction 2 hours, obtaining degree of functionality is 5.0, the described PPG I that hydroxyl value is 370mgKOH/g.
Prepare PPG II, process is as follows again:
(1) take ethylene glycol 40g and magnesium chloride 3g in 200g peanut oil, controlling reaction temperature is 120 DEG C, react 3 hours,To modification peanut oil;
(3) modification peanut oil 100g and Pd-Fe catalyst 0.08g are mixed in reactor, controlling reaction temperature is 150 DEG C,Reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add expoxy propane 8g, atmospheric closed reaction 2 hours, obtains officialEnergy degree is 5.5, the described PPG II that hydroxyl value is 360mgKOH/g.
A kind of hard-foam polyurethane insulation material, described insulation material is obtained by the raw material mixed foaming of following weight fraction:Take PPG I 70g, PPG II 20g, 70 order expanded vermiculite 5g, hollow mesoporous silica nanospheres 7g, twoChlorine fluoroethane 10g, diethanol monoisopropanolamine 5g and 3-[MPEG-550] propyl trialkoxy silane 2g mixing is allEven, then, with dimer acid diisocyanate 80g mixed foaming, after overcuring, can obtain hard-foam polyurethane of the present inventionInsulation material.
The physical function parameter of the hard-foam polyurethane insulation material respectively embodiment 1-4 being prepared detects, and surveysTest result is as shown in table 1.
Table 1
From table, thermal conductivity factor, compression strength, the stretching of hard-foam polyurethane insulation material prepared by the above embodiment of the present inventionThe indexs such as adhesion strength, dimensional stability and rate of closed hole all have significantly and improve than existing insulation material, through freezing or highUnder temperature condition, without phenomenons such as contraction, distortion, expansion, crackings, be a kind of insulation material of excellent performance.
The present invention is not limited to aforesaid detailed description of the invention. The present invention expands to any disclosure in this manualNew feature or any new combination, and the arbitrary new method disclosing or step or any new combination of process.
Claims (8)
1. a hard-foam polyurethane insulation material, is characterized in that, described insulation material is mixed by the raw material of following weight fractionFoam and obtain: 70 ~ 100 parts of isocyanates, 40 ~ 80 parts of PPG I, 10 ~ 30 parts of PPG II, expanded vermiculite 3 ~ 6Part, 5 ~ 8 parts of nano silicons, 10 ~ 20 parts of blowing agents, 1 ~ 5 part of catalyst, 3-[MPEG-550] propyl group three alcoxyls1 ~ 5 part of base silane; Described PPG I is lignin polyether polyalcohol, and described PPG II is by modification peanut oilFor initiator, expoxy propane are the PPG that polymerization single polymerization monomer is polymerized.
2. hard-foam polyurethane insulation material according to claim 1, is characterized in that: described isocyanates is dimeric dibasic acid twoIsocyanates, 1, one or more in hexamethylene-diisocyanate, toluene di-isocyanate(TDI) or '-diphenylmethane diisocyanate.
3. hard-foam polyurethane insulation material according to claim 1, is characterized in that: the particle diameter of described expanded vermiculite is 40~ 70 orders.
4. hard-foam polyurethane insulation material according to claim 1, is characterized in that: described nano silicon is dioxySiClx nano wire or hollow mesoporous silica nanospheres.
5. hard-foam polyurethane insulation material according to claim 1, is characterized in that: described blowing agent is that a fluorine dichloro is ownOne or more in alkane, F-11, dichlorodifluoromethane, chlorodifluoroethane and chloro fluoroethane.
6. hard-foam polyurethane insulation material according to claim 1, is characterized in that: described catalyst is diethanol Dan YiPropanolamine or AEEA.
7. according to the hard-foam polyurethane insulation material described in claim 1 to 6 any one claim, it is characterized in that: described inThe degree of functionality of PPG I is 4.5 ~ 5.0, and its hydroxyl value is 370 ~ 410mgKOH/g, and it is according to the raw material of following parts by weightMake with method:
(1) take 50 ~ 100 parts, lignin, 30 ~ 50 parts, water, 1 ~ 5 part of lignin peroxidase, 1 ~ 3 part of catalase, furanMutter 3 ~ 10 parts of 1 ~ 10 part, acetaldehyde and furfuryl alcohols in reactor, and reaction temperature is 80 DEG C, and stirring reaction 5 hours, obtains enzymolysis modifiedLignin;
(2) by 100 parts, enzymolysis modified lignin, 250 ~ 350 parts of glycerine, 100 ~ 300 parts of diethylene glycol (DEG)s and Pd-Fe catalyst 0.01~ 0.05 part is mixed in reactor, and controlling reaction temperature is 120 DEG C, is reacted by the logical nitrogen bubble of reactor bottom, then takes out trueSky, adds 2 ~ 10 parts of expoxy propane, and atmospheric closed reaction 2 hours, obtains described PPG I.
8. according to the hard-foam polyurethane insulation material described in claim 1 to 6 any one claim, it is characterized in that: described inThe degree of functionality of PPG II is 5.0 ~ 6.0, and its hydroxyl value is 360 ~ 430mgKOH/g, and it is according to the raw material of following parts by weightMake with method:
(1) take in 1 ~ 5 part to 100 ~ 300 portions peanut oil of 20 ~ 50 parts of ethylene glycol and magnesium chloride, controlling reaction temperature is 120 DEG C,React 3 hours, obtain modification peanut oil;
(2) 0.05 ~ 1.0 part of 100 parts of modification peanut oil and Pd-Fe catalyst is mixed in reactor, controls reaction temperature and be150 DEG C, reacted by the logical nitrogen bubble of reactor bottom, then vacuumize, add 2 ~ 10 parts of expoxy propane, atmospheric closed reaction 2Hour, obtain described PPG II.
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| CN201610074102.7A CN105601868A (en) | 2016-02-03 | 2016-02-03 | Rigid foam polyurethane thermal insulation material |
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| CN106366282A (en) * | 2016-09-21 | 2017-02-01 | 青岛德隆装备有限公司 | Polyurethane soft-hard foam combined forming process for beer barrel |
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| CN112442269A (en) * | 2020-10-30 | 2021-03-05 | 苏州市雄林新材料科技有限公司 | Environment-friendly TPU (thermoplastic polyurethane) film/porous nano composite material and preparation method thereof |
| CN116515069A (en) * | 2023-04-10 | 2023-08-01 | 天长市伯士的环保新材料有限公司 | Polyurethane hard foam raw material composition, polyurethane hard foam and preparation method of polyurethane hard foam |
| CN116515069B (en) * | 2023-04-10 | 2023-11-14 | 天长市伯士的环保新材料有限公司 | Polyurethane hard foam raw material composition, polyurethane hard foam and preparation method of polyurethane hard foam |
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Application publication date: 20160525 |